CN106928406A - A kind of adhesive polyester of adjustable viscosity and preparation method thereof - Google Patents
A kind of adhesive polyester of adjustable viscosity and preparation method thereof Download PDFInfo
- Publication number
- CN106928406A CN106928406A CN201710164997.8A CN201710164997A CN106928406A CN 106928406 A CN106928406 A CN 106928406A CN 201710164997 A CN201710164997 A CN 201710164997A CN 106928406 A CN106928406 A CN 106928406A
- Authority
- CN
- China
- Prior art keywords
- acid
- polyester
- matrix resin
- dicarboxylic acid
- adjustable viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 29
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000011159 matrix material Substances 0.000 claims abstract description 31
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 150000001298 alcohols Chemical class 0.000 claims abstract description 7
- 230000006837 decompression Effects 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- LGCRPKOHRIXSEG-UHFFFAOYSA-N (4-methoxyphenyl)-phenyldiazene Chemical compound C1=CC(OC)=CC=C1N=NC1=CC=CC=C1 LGCRPKOHRIXSEG-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- -1 4- hydroxyazo phenyl Chemical group 0.000 claims description 5
- 239000001530 fumaric acid Substances 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract 2
- 238000011282 treatment Methods 0.000 description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920000305 Nylon 6,10 Polymers 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical class [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- 125000005395 methacrylic acid group Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a kind of adhesive polyester of adjustable viscosity and preparation method thereof, the adhesive polyester number-average molecular weight is 10,000 50000, the 5mg KOH/g of acid number 1, the 50mg KOH/g of hydroxyl value 10.Its preparation method first passes through saturated dicarboxylic acid, the combination of unsaturated dicarboxylic acid and dihydroxylic alcohols and carries out esterification, then obtains matrix resin by decompression polycondensation；Graft reaction finally is carried out to matrix resin, obtained matrix resin and the monomer containing azobenzene structure are carried out into graft reaction, obtain polyester.Present invention utilizes the photo-isomerisable characteristic of azobenzene, causing the adhesion strength of final products reduces, and reaches the effect of composite bed separation, realizes reversible adhesion repeatedly.
Description
Technical field
The invention belongs to adhesive synthesis field, and in particular to a kind of adjustable adhesive polyester of viscosity and its preparation side
Method.
Background technology
The reversible of adhesive is bonded in many fields and all plays a very important role, such as auto industry, semiconductor electronic, build
Build, secret machinery etc..
Method conventional at present is mainly and is initially formed cross-linked structure by the chemical reaction of adhesive component, then by it
Its method destroys the cross-linked structure to realize.If US2005/0159521 is by the radical crosslinking with light radiation exposure, so
Afterwards with the binding system of ultrasound destruction, reversible bonding is realized, but after the completion of a process, it is impossible to continue reversible implementation.
Also by the chemical constitution for forming thermally labile, such as steric hindrance urea groups, then by heating up, destroy the structure, from
And realize the decline of cohesive force.But these are irreversibly.
The content of the invention
The invention provides a kind of adhesive polyester of adjustable viscosity and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of adhesive preparation process of polyester of adjustable viscosity, comprises the following steps,
S1, prepare matrix resin, first pass through saturated dicarboxylic acid, the combination of unsaturated dicarboxylic acid and dihydroxylic alcohols be esterified it is anti-
Should, then obtain matrix resin by decompression polycondensation again；The saturated dicarboxylic acid accounts for synthesis matrix resin total dicarboxylic acid and always rubs
You are ratio 70-90%, and the unsaturated dicarboxylic acid accounts for synthesis matrix resin total dicarboxylic acid total moles ratio 10-30%；
S2, graft reaction is carried out to matrix resin, matrix resin obtained in S1 is connect with the monomer containing azobenzene structure
Branch reaction, obtains the adhesive polyester of adjustable viscosity.
Preferably, the S1 comprises the following steps：
S11, saturated dicarboxylic acid, the combination of unsaturated dicarboxylic acid and dihydroxylic alcohols are carried out into esterification under nitrogen atmosphere,
Reaction temperature is maintained between 220-255 DEG C；
S12, after the accessory substance of esterification in S11 reaches theoretical value, heat up keep reaction temperature between 250-280 DEG C,
Under vacuum, decompression polycondensation is carried out；
S13, after the completion of polycondensation reaction in S12, be filled with nitrogen and eliminate vacuum, extruding and discharging is obtained matrix resin.
Preferably, the S2 comprises the following steps：
S21, the matrix resin that will be prepared dissolving are made the solution that solids content is 50%, add initiator, and protect in nitrogen
60-70 DEG C of reaction 2h is warming up under shield；
S22, to S21 product precipitation purifications, vacuum drying is obtained the adhesive polyester of adjustable viscosity.
Preferably, the saturated dicarboxylic acid in the S1 is selected from：Terephthalic acid (TPA), M-phthalic acid, phthalic acid, third
Diacid, adipic acid, azelaic acid, decanedioic acid, phthalic anhydride, 1,4 cyclohexanedicarboxylic acid, naphthalene diacid one kind therein or one
Plant combination of the above.
Preferably, unsaturated dicarboxylic acid is selected from the S1：One or more groups in fumaric acid, maleic acid
Close.
Preferably, dihydroxylic alcohols is selected from the S1：Ethylene glycol, BDO, 1,3-PD, 1,2-PD, newly
Pentanediol, hexylene glycol, 1,4-CHDM, one or more combinations in polyethylene glycol.
Preferably, the monomer containing azobenzene structure is selected from the S2：Methacrylic acid [6- (4- Methoxy-azobenzenes
Base -4 '-epoxide) hexyl] ester, acrylic acid [6- (4- Methoxy-azobenzenes base -4 '-epoxide) hexyl] ester, methacrylic acid [6-
(- 4 '-epoxide of 4- methyl- phenyl) hexyl] ester, methacrylic acid [6- (- 4 '-epoxide of 4- hydroxyazo phenyl) octyl group] ester,
One or more combinations therein of methacrylic acid [6- (- 4 '-epoxide of 4- hydroxyazo phenyl) octyl group] ester.
Preferably, including adhesive polyester number-average molecular weight is 10000-50000, acid number 1-5mg KOH/g, hydroxyl value
10-50mg KOH/g。
The present invention is that azobenzene structure polymer is widely closed due to its unique photo-isomerisable performance using principle
Note, in optics, crystal structure, the aspect such as gel has all multipurposes.Azobenzene polymer can occur under the irradiation of light can
Inverse cis-trans isomerism, has very big influence, especially optical property and crystal property to the structure and performance of polymer,
The glass transition temperature of polymer can also be influenceed simultaneously, changes the form of polymer, change the cohesive force and chain of glue-line
Section arrangement, so can at ambient temperature realize the viscosity control of adhesive by illumination.
Beneficial effects of the present invention are embodied in：Polyester adhesive resin of the synthesis side chain with azobenzene, using azo
The photo-isomerisable characteristic of benzene：In the case where wavelength is 540nm illumination, azobenzene is the very strong transconfiguration of rigidity, and product vitrifying turns
Temperature is higher, there is preferable cohesive force and adhesion strength；And after using wavelength 365nm treatment with ultraviolet light, azobenzene
Switch to cis by trans, the glass transition temperature of product drops to below room temperature, at ambient temperature with certain viscoelastic
Property, so as to change the change of molecule arranging structure, decline cohesive force, causing the adhesion strength of product reduces, and reaches composite bed
The effect of separation, realizes reversible adhesion repeatedly.
Specific embodiment
Technical scheme is specifically described with reference to embodiments.
The synthesis of adhesive resin
Example one
A）, polyester matrix resin preparation：
By 1.66kg terephthalic acid (TPA)s, 3.32kg M-phthalic acids, 7.31kg adipic acids, 2.32kg maleic acids, 6.08kg second two
Alcohol, 4.96kg hexylene glycols and 4.4g isopropyl titanates are put into reactor.Air is discharged with nitrogen displacement, stirring is warming up to
Esterification is carried out between 220-255 DEG C.After accessory substance reaches theoretical value, heat up keep reaction temperature 250-280 DEG C it
Between, polycondensation of depressurizing stops reaction after reaching terminal, is filled with nitrogen and eliminates vacuum, and extruding and discharging obtains matrix resin.
B）, graft reaction：
The matrix resin that will be prepared is dissolved in butanone, is made the solution of solids content 50%, adds 16g initiator azos
Bis-isobutyronitrile, 7.92kg methacrylic acids [6- (- 4 '-epoxide of 4- Methoxy-azobenzene bases) hexyl] ester is well mixed, Ran Hou
Under the protection of nitrogen, 60-70 DEG C of reaction 2h is warmed up to.After n-hexane precipitation purification, vacuum drying obtains adhesive polyester.
Example two
A）, polyester matrix resin preparation：
By 1.66kg terephthalic acid (TPA)s, 3.32kg M-phthalic acids, 10.1kg decanedioic acid, 2.32kg maleic acids, 6.08kg second two
Alcohol, 4.37kg neopentyl glycols and 3.5g antimony acetates are put into reactor.Air is discharged with nitrogen displacement, stirring is warming up to
Esterification is carried out between 220-255 DEG C.After accessory substance reaches theoretical value, heat up keep reaction temperature 250-280 DEG C it
Between, polycondensation of depressurizing stops reaction after reaching terminal, is filled with nitrogen and eliminates vacuum, and extruding and discharging obtains matrix resin.
B）, graft reaction：
The matrix resin that will be prepared is dissolved in toluene, is made the solution of solids content 50%, adds 16g initiator azos
Bis-isobutyronitrile, 9.53kg acrylic acid [6- (- 4 '-epoxide of 4- Methoxy-azobenzene bases) hexyl] ester is well mixed, then in nitrogen
Protection under, be warmed up to 60-70 DEG C reaction 2h.After n-hexane precipitation purification, vacuum drying obtains adhesive polyester.
Example three
A）, polyester matrix resin preparation：
By 4.15kg M-phthalic acids, 10.1kg decanedioic acid, 2.9kg fumaric acid, 11.5kg hexylene glycols, 4.37kg neopentyl glycols with
And during 3.5g antimony acetates put into reactor.Air is discharged with nitrogen displacement, stirring is esterified between being warming up to 220-255 DEG C
Reaction.After accessory substance reaches theoretical value, heat up and keep reaction temperature between 250-280 DEG C, polycondensation of depressurizing, after reaching terminal
Stop reaction, be filled with nitrogen and eliminate vacuum, extruding and discharging obtains matrix resin.
B）, graft reaction：
The matrix resin that will be prepared is dissolved in butanone, is made the solution of solids content 50%, adds 16g initiator azos
Bis-isobutyronitrile, 9.53kg acrylic acid [6- (- 4 '-epoxide of 4- Methoxy-azobenzene bases) hexyl] ester is well mixed, then in nitrogen
Protection under, be warmed up to 60-70 DEG C reaction 2h.After n-hexane precipitation purification, vacuum drying obtains adhesive polyester
Example four
A）, polyester matrix resin preparation：
By 4.15kg1,4- cyclohexane cyclohexanedimethanodibasics, 10.1kg decanedioic acid, 3.48kg fumaric acid, 11.6kg1,4- butanediols,
4.37kg neopentyl glycols and 3.5g antimony acetates are put into reactor.Air is discharged with nitrogen displacement, stirring is warming up to 220-
Esterification is carried out between 255 DEG C.After accessory substance reaches theoretical value, heat up and keep reaction temperature between 250-280 DEG C, subtract
Compression is poly-, and reaction is stopped after reaching terminal, is filled with nitrogen and eliminates vacuum, and extruding and discharging obtains matrix resin.
B）, graft reaction：
The matrix resin that will be prepared is dissolved in butanone, is made the solution of solids content 50%, adds 16g initiator azos
Bis-isobutyronitrile, 9.18kg methacrylic acids [6- (- 4 '-epoxide of 4- hydroxyazo phenyl) octyl group] ester is well mixed, then in nitrogen
Under the protection of gas, 60-70 DEG C of reaction 2h is warmed up to.After n-hexane precipitation purification, vacuum drying obtains adhesive polyester.
Comparative example
By 4.15kg1,4- cyclohexane cyclohexanedimethanodibasics, 10.1kg decanedioic acid, 3.48kg fumaric acid, 11.6kg1,4- butanediols,
4.37kg neopentyl glycols and 3.5g antimony acetates are put into reactor.Air is discharged with nitrogen displacement, stirring is warming up to 220-
Esterification is carried out between 255 DEG C.After accessory substance reaches theoretical value, heat up and keep reaction temperature between 250-280 DEG C, subtract
Compression is poly-, and reaction is stopped after reaching terminal, is filled with nitrogen and eliminates vacuum, and extruding and discharging obtains comparative example resin.
The measure of number-average molecular weight
Using GPC（Gel permeation chromatography）The number-average molecular weight of polymer is determined, is measured using waters companies GPC,
In tetrahydrofuran at 30 DEG C（ THF）In, relatively a series of polystyrene standards carry out the measurement.
The test of glass transition temperature
Tested using the DSC of TA companies, test sample is 540nm in wavelength respectively, and light intensity is 5mW*cm-2Light treatment
Afterwards, with wavelength it is again 365nm and after first time light irradiation, light intensity is 70mW*cm-2Ultraviolet light 20min after
Glass transition temperature (Tg).
The apparent observation of sample
Apparent condition of the sample after photo-irradiation treatment twice is observed by the naked eye, and its hardness mobility is touched with hand pressing.
Above test performance result is as shown in table 1.
Table 1：Embodiment is contrasted with comparative example product index：
| Numbering | Number-average molecular weight | Tg (irradiates) for the first time | Tg (second irradiation) |
| Embodiment one | 12000 | 23℃ | -15℃ |
| Embodiment two | 35000 | 40℃ | 5.8℃ |
| Embodiment three | 40000 | 32℃ | -7.5℃ |
| Example IV | 22000 | 36℃ | -21℃ |
| Comparative example | 30000 | 32℃ | 32℃ |
Drawn from data above, by being processed for light after adhesion layer sample glass transition temperature analysis, sample exists
After 540nm photo-irradiation treatments, azobenzene structure is transconfiguration（trans）, integral rigidity is very strong, so glass transition temperature ratio
Higher, sample keeps solid state at room temperature, and cohesive force is stronger.Then there is photo-isomerisable with after treatment with ultraviolet light again,
Azobenzene structure for the first time process after it is trans switch to it is cis（cis）, overall Tg reduction, less than room temperature, now adhesion layer resin
There are certain mobile performance, segment activity, cohesive force reduction at ambient temperature so that adhesion property reduction, composite bed is easy
Separate.
Adhesiveness is tested
The resin of four embodiments and comparative example is combined with PET film and tinplate sheet respectively, the resin that will be obtained is molten
Solution is configured to the solution of solid content 30% in ethyl acetate solvent, is then coated with tinplate, and applying glue solids content is
10g/m2, then composite transparent polyethylene terephthalate（PET）Film, dries 10 minutes at 80 DEG C, is with wavelength first
540nm, light intensity is 5mW*cm-2Light irradiation 20min after, cut 15mm × 200mm batten, using instron,
At 25 DEG C, 180 ° of disbonded tests are carried out with the test speed of 50mm/min.
The composite bed that will be crossed through first time treatment with irradiation is 365nm using wavelength, and light intensity is 70mW*cm-2Ultraviolet lighting
Penetrating 20min carries out second treatment with irradiation, is then cut to the batten of 15mm × 200mm, using instron, 25
DEG C, 180 ° of disbonded tests are carried out with the test speed of 50mm/min, contrast as shown in table 2.
Table 2：Embodiment is contrasted with comparative example product property：
| Numbering | Peeling force after first time photo-irradiation treatment（N/mm） | Peeling force after second photo-irradiation treatment（N/mm） |
| Embodiment one | 3.7 | 0.7 |
| Embodiment two | 4.5 | 0.4 |
| Embodiment three | 4.2 | 0.65 |
| Example IV | 4.4 | 0.9 |
| Comparative example | 4.2 | 4.2 |
By the test analysis of the peeling force after different photo-irradiation treatments, by after first time photo-irradiation treatment, composite bed has
Preferable peel strength, sample adhesion is stronger.After second photo-irradiation treatment, because the structure of sample changes, its
Peeling force is greatly reduced, and composite bed can be separated easily, be reprocessed.
The present invention still has various specific embodiments.All use equivalents or equivalent transformation and all skills for being formed
Art scheme, all falls within the scope of protection of present invention.
Claims (8)
1. a kind of adhesive preparation process of polyester of adjustable viscosity, it is characterised in that：Comprise the following steps,
S1, prepare matrix resin, first pass through saturated dicarboxylic acid, the combination of unsaturated dicarboxylic acid and dihydroxylic alcohols be esterified it is anti-
Should, then obtain matrix resin by decompression polycondensation again；The saturated dicarboxylic acid accounts for synthesis matrix resin total dicarboxylic acid and always rubs
You are ratio 70-90%, and the unsaturated dicarboxylic acid accounts for synthesis matrix resin total dicarboxylic acid total moles ratio 10-30%；
S2, graft reaction is carried out to matrix resin, matrix resin obtained in S1 is connect with the monomer containing azobenzene structure
Branch reaction, obtains the adhesive polyester of adjustable viscosity.
2. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, it is characterised in that：The S1 bags
Include following steps：
S11, saturated dicarboxylic acid, the combination of unsaturated dicarboxylic acid and dihydroxylic alcohols are carried out into esterification under nitrogen atmosphere,
Reaction temperature is maintained between 220-255 DEG C；
S12, after the accessory substance of esterification in S11 reaches theoretical value, heat up keep reaction temperature between 250-280 DEG C,
Under vacuum, decompression polycondensation is carried out；
S13, after the completion of polycondensation reaction in S12, be filled with nitrogen and eliminate vacuum, extruding and discharging is obtained matrix resin.
3. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, it is characterised in that：The S2 bags
Include following steps：
S21, the matrix resin that will be prepared dissolving are made the solution that solids content is 50%, add initiator, and protect in nitrogen
60-70 DEG C of reaction 2h is warming up under shield；
S22, to S21 product precipitation purifications, vacuum drying is obtained the adhesive polyester of adjustable viscosity.
4. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, it is characterised in that：In the S1
Saturated dicarboxylic acid be selected from：Terephthalic acid (TPA), M-phthalic acid, phthalic acid, malonic acid, adipic acid, azelaic acid, the last of the ten Heavenly stems two
Acid, phthalic anhydride, 1,4 cyclohexanedicarboxylic acid, one or more combinations therein of naphthalene diacid.
5. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, it is characterised in that：In the S1
Unsaturated dicarboxylic acid is selected from：One or more combinations in fumaric acid, maleic acid.
6. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, it is characterised in that：In the S1
Dihydroxylic alcohols is selected from：Ethylene glycol, BDO, 1,3-PD, 1,2-PD, neopentyl glycol, hexylene glycol, Isosorbide-5-Nitrae-hexamethylene
Dimethanol, one or more combinations in polyethylene glycol.
7. a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 2, it is characterised in that：In the S2
Monomer containing azobenzene structure is selected from：Methacrylic acid [6- (- 4 '-epoxide of 4- Methoxy-azobenzene bases) hexyl] ester, propylene
Sour [6- (- 4 '-epoxide of 4- Methoxy-azobenzene bases) hexyl] ester, methacrylic acid [6- (- 4 '-epoxide of 4- methyl- phenyl)
Hexyl] ester, methacrylic acid [6- (- 4 '-epoxide of 4- hydroxyazo phenyl) octyl group] ester, methacrylic acid [6- (4- hydroxyazos
Phenyl -4 '-epoxide) octyl group] ester one or more combinations therein.
8. polyester obtained in a kind of adhesive preparation process of polyester of adjustable viscosity as claimed in claim 1, its feature exists
In：The adhesive polyester number-average molecular weight is 10000-50000, acid number 1-5mg KOH/g, hydroxyl value 10-50mg KOH/g.
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| EP3696200A1 (en) * | 2019-02-14 | 2020-08-19 | Konica Minolta, Inc. | Photoresponsive high-molecular weight material, adhesive, toner, and image forming method |
| CN113817146A (en) * | 2021-08-09 | 2021-12-21 | 浙江乘鹰新材料股份有限公司 | Polyester resin and preparation method and application thereof |
| CN114031759A (en) * | 2021-12-10 | 2022-02-11 | 盐城市恒丰海绵有限公司 | Unsaturated fatty diacid-based polyester polyol and preparation method thereof |
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| CN113817146A (en) * | 2021-08-09 | 2021-12-21 | 浙江乘鹰新材料股份有限公司 | Polyester resin and preparation method and application thereof |
| CN114031759A (en) * | 2021-12-10 | 2022-02-11 | 盐城市恒丰海绵有限公司 | Unsaturated fatty diacid-based polyester polyol and preparation method thereof |
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